CN100513430C - Preparation method of core-shell type emulsion particle emulsion for enhancing rubber - Google Patents
Preparation method of core-shell type emulsion particle emulsion for enhancing rubber Download PDFInfo
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- CN100513430C CN100513430C CNB2007100648512A CN200710064851A CN100513430C CN 100513430 C CN100513430 C CN 100513430C CN B2007100648512 A CNB2007100648512 A CN B2007100648512A CN 200710064851 A CN200710064851 A CN 200710064851A CN 100513430 C CN100513430 C CN 100513430C
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Abstract
A kind of core-shell rubber latex particles emulsion for increasing rubber and its preparation is through emulsion polymerization obtaining monodisperse latex particles, then using seed emulsion polymerization to get the core-shell rubber particles emulsion. The core-shell latex particles has spherical inspection and nano-scale, ensures reinforcement capability, and at the same time, makes rubber reduced density, good mobility, small high-stress concentration, and uniform stress distribution, and because of good interface, it can improve the mechanical properties effectively.
Description
Technical field:
The present invention relates to a kind of preparation method who is used for rubber enhanced core-shell type emulsion particle emulsion.
Background technology:
The widely used filling toughener of elastomeric material is carbon black, white carbon black, lime carbonate, potter's clay, talcum powder, carclazyte, tripoli, clay or the like.This wherein, carbon black is the toughener that depends on petroleum resources, the filler of other kind derives from natural basically.Carbon black and white carbon black be because particle meticulous (size of other primary partical of some grade is less than 20 nanometers), thereby be the of paramount importance toughener of rubber.The toughener of other kind often is counted as weighting agent because particle is thick, improve elastomeric material processing characteristics, reduce cost and auxiliary to a certain extent enhancing the (the logical toughener of being called).Although above these tougheners play an important role in rubber industry, the density of all tougheners that current rubber industry is used is all at 1.7g/cm
3More than, and the density of conventional rubber rubber is generally all at 1.1g/cm
3Below.This makes the density of the elastomeric material that toughener is filled significantly increase, thereby makes macromolecular material lose the characteristic of light weight to a certain extent.As: it strengthens the weight of rubber soles, and the weight of tire is improved or the like, and for material for sole of shoe, people always wish it under the prerequisite that keeps primary characteristic, and light as much as possible, particularly for military footwear, this point is very important; For tire industry, under the prerequisite that guarantees the every use properties of tire, the oil consumption of tire is reduced by various technique means as much as possible, be beneficial to environment protection and save petroleum resources.This wherein, alleviating of the weight of tyre rubber is one of important measures, the tire lightweight can make the fuel-economizing index of automobile obviously improve.For developing electromobile, the light-weighted importance of tire is mathematical especially.
For these reasons, rubber with the demand for development of filling toughener is: high reinforcement, polymolecularity, low density, low price.The primary partical size of high reinforcement requirement toughener (or the size of particles after being dispersed in the rubber) must be little, dispersion will be got well, and directly or indirectly (refer to add by surface treatment or in rubber coupling agent etc. the back) effect between the rubber matrix macromole is eager to excel.Low density then is decided by the true density of toughener fully, is decided by the materialization structure of toughener.Low price then requires it to draw materials conveniently, makes simply, and the source is abundant.As everyone knows, the density of most inorganic materials is very high.Therefore, the development new packing can and synthesize angle and be implemented from the polymer design, promptly prepares HR highly reinforcing organic polymer filler, replaces existing inorganic mineral filler.
Summary of the invention:
The purpose of this invention is to provide a kind of preparation method who is used for rubber enhanced core-shell type emulsion particle emulsion.Hud typed latex particle has nanoscale, sphericity height, low density characteristic, when guaranteeing reinforcing property, makes the rubber item density of having filled this particle low, and mechanical property is good, and the high stress concentrations district is few, and stress distribution is even, and interface junction gets togather.
A kind of preparation method who is used for rubber enhanced core-shell type emulsion particle emulsion of the present invention:
The first step: under agitation condition, in reactor, add deionized water, emulsifying agent, vinyl monomer, polyenoid class cross-linking monomer successively and carry out emulsification, be heated to 70～85 ℃, add the initiator initiated polymerization, regulate pH=7, finished stratum nucleare particle building-up reactions, and obtained examining emulsion in 6-8 hour;
The mass ratio of used vinyl monomer, polyenoid class cross-linking monomer, initiator is 40～55:10～16:0.3～0.6.
Said vinyl monomer is any in the following material or their combination: vinylbenzene, methyl methacrylate, alpha-methyl styrene, glycidyl methacrylate, uncle's hendecoic acid vinyl acetate, acrylonitrile monemer.
Polyenoid class cross-linking monomer is any in the following material or their combination: Vinylstyrene, bisacrylamide, ethylene glycol dimethacrylate, tirethylene glycol dimethacrylate.
Second step: under agitation condition, in autoclave, add nuclear emulsion (the first step makes), shell diolefinic monomer, emulsifying agent, water and initiator successively, under agitation condition, carry out emulsification, regulate pH=7,450-550 kPa of reactor pressurization, swelling 1～3 hour is warming up to 70～85 ℃, reacts 6-8 hour; Obtain core-shell type emulsion particle emulsion.
The mass ratio of used nuclear emulsion (the first step makes), dienes monomer, initiator is 150～200:10～30:0.3～0.6.
Shell monomers is any in the following material or their combination: isoprene, divinyl, butadiene oligomer.
The used initiator of preparation emulsion particle emulsion is Potassium Persulphate, Sodium Persulfate, ammonium persulphate, Potassium Persulphate-sodium bisulfite, Sodium Persulfate-sodium bisulfite or ammonium persulfate-sodium bisulfite.The consumption of initiator in the first step reaction is 0.7%～1.2% of vinyl monomer quality, and the consumption in the reaction of second step is 1%～2% of a dienes soft monomer quality.
Preparation emulsion particle emulsion used emulsifying agent is letex polymerization anionic emulsifier, nonionic emulsifier, a negatively charged ion-non-ionic composite emulsifying agent commonly used, respectively as: sodium laurylsulfonate (SDS), alkylphenol polyoxyethylene series (as OP-10), SDS/OP-10 are compound.
The present invention is used for rubber enhanced core-shell type emulsion particle emulsion and can be used as the rubber reinforcing filler, to improve the performance of rubber.Usually adopt following two kinds of addition meanss:
First method: the latex coprecipitation method, what proportionally will make is used for rubber enhanced core-shell type emulsion particle emulsion and SBR emulsion or acrylonitrile-butadiene rubber latex uniform mixing, uses 5%CaCl again
2With the blended liquid breakdown of emulsion.
Second method: melt-blending process, be used for the direct breakdown of emulsion of rubber enhanced core-shell type emulsion particle emulsion with what make, obtain solid particulate, again with itself and butadiene-styrene latex or butyronitrile latex mechanical stirring, uniform mixing.
Above-mentioned two kinds of methods all need to make required elastomeric material again after conventional method sulfuration.
Effect of the present invention: the rubber enhanced core-shell type emulsion particle emulsion that is used for of the present invention is nuclear with the cross-linked polymer, is the mixture of shell with the dienes monomer, the structure that has the stone soft shell, not only can play the effect of stone Reinforced Rubber, and, can in matrix, keep excellent dispersion state because soft shell has good consistency with rubber matrix.This nano-scale nucleocapsid latex particle is packed in the rubber, reaches and improve it and combine, reduce targets such as rubber item density, raising rubber item mechanical property with interface between rubber matrix.
Shell unsaturated elastic body and base rubber produce covalent bonds when sulfuration, eliminated interface region friction and hysteresis phenomenon to greatest extent; Of light color, can prepare transparent or brightly painted rubber item; Core-shell type emulsion particle emulsion enhanced rubber composite belongs to overall height molecular material goods, reclaims easily.
Description of drawings:
Fig. 1: be the polystyrene core emulsion latex particle photo among the embodiment 1 that takes with the XL-30 field launch environment scanning electron microscope (ESEM) that U.S. FEI Co. makes, wherein the particle diameter of latex particle is between 30～60nm.
Fig. 2: be the hud typed latex particle photo of polystyrene/isoprene among the embodiment 1 that takes with the XL-30 field launch environment scanning electron microscope (ESEM) that U.S. FEI Co. makes equally, wherein the particle diameter of nucleocapsid latex particle is between 60～90nm.
Embodiment:
The first step: the preparation of nuclear emulsion
Press the prescription of table 1, in reactor, add emulsifying agent sodium laurylsulfonate (SDS)/alkylphenol polyoxyethylene series (OP-10) and deionized water, stirring makes emulsifier mix even, add styrene monomer (St) and Vinylstyrene (DVB), stirring makes monomer emulsification, stablized after being warming up to 70 ℃ 10 minutes, with initiator potassium persulfate (KPS) with adding behind the deionized water dissolving.Holding temperature adds pH regulator agent sodium bicarbonate (NaHCO simultaneously
3), regulate pH=7; Reacted 8 hours, this moment, the monomer residue smell disappeared substantially, stopped polymerization.
The basic components of the monodisperse cross-linked polystyrene latex of table 1 preparation
| Raw material | Quality (g) |
| Monomer: St polyenoid class cross-linking monomer: DVB initiator: KPS emulsifying agent: OP-10 SDS H 2O | 52.5 10.5 0.53 1.75 3.5 210 |
Second step: the preparation of core-shell type emulsion particle emulsion
Press table 2 prescription under agitation condition, emulsion (the first step makes), isoprene (Is) are examined in adding in autoclave, (elder generation adds 2/3 to add emulsifier op-10/SDS at twice, emulsification adds in addition 1/3 again after 30 minutes), water, fully emulsified back adds initiator potassium persulfate KPS, with sodium bicarbonate (NaHCO
3) regulate pH=7, to pressurize 500 kPas, swelling 2 hours is warming up to 70 ℃, reacts 8 hours; Obtain core-shell type emulsion particle emulsion.
The prescription of the hud typed latex particle of table 2 preparation
| Raw material | Quality (g) |
| Monomer: Is examines emulsion: emulsifying agent: OP-10 SDS initiator: KPS H 2O | 30 200 1 2 0.3 200 |
By above two the step prepare particle diameter at 60～90nm, solid content is 19% hud typed latex particle.Wherein stratum nucleare is 5: 3 with the ratio of shell monomers.
Hud typed latex filler dosing in styrene-butadiene rubber(SBR)
First method: the latex coprecipitation method, respectively according to 1: 10 mass ratio with the core-shell type emulsion particle emulsion and the SBR emulsion uniform mixing that make, use 5%CaCl again
2With the blended liquid breakdown of emulsion, every performance of test styrene-butadiene rubber(SBR) after vulcanizing.
Second method: melt-blending process, be used for the direct breakdown of emulsion of rubber enhanced core-shell type emulsion particle emulsion with what make, obtain solid particulate, again with itself and butadiene-styrene latex with 1: 10 quality than mechanical stirring, uniform mixing.After vulcanizing, test every performance of styrene-butadiene rubber(SBR) then.
The styrene-butadiene rubber(SBR) mechanical property that different fillers of table 3 and addition methods obtain relatively
The data of table 3 show with respect to all fillers of pure styrene-butadiene rubber(SBR) (SBR) and all show tangible reinforced effects, wherein adopt the latex coprecipitation method to dose comprehensive mechanical property the best of the styrene-butadiene rubber(SBR) of hud typed latex particle.Reason is the hud typed latex particle of nano level of this stone soft shell structure, not only can play the effect of stone Reinforced Rubber, and soft shell has good consistency with rubber matrix, and is crosslinked by chemical bond with rubber matrix, keeps excellent dispersion state in matrix; The principle that meets the rubber reinforcing filler three elements fully, promptly particle diameter, structural, surfactivity are three important factors that influence the strengthening agent reinforced effects.In addition, can also see from table 3: dose the hud typed latex particle of identical composition and umber, every mechanical property of the styrene-butadiene rubber(SBR) that the latex coprecipitation method makes is better than the styrene-butadiene rubber(SBR) performance that melt-blending process makes.Its reason is: the general about 100nm of butadiene-styrene latex particle dia, the latex particle that makes among the present invention are between 50nm～80nm, and therefore, the latex filler grain is good and butadiene-styrene latex particle formation IPN and isolation at the aqueous phase energy, reaches nano level and disperses.
Embodiment 2
The first step: the preparation of nuclear emulsion
The preparation method is with embodiment 1, feeds intake by the proportioning raw materials of table 4.
The basic components of the monodisperse cross-linked polystyrene latex of table 4 preparation
| Raw material | Quality (g) |
| Monomer: St polyenoid class cross-linking monomer: DVB initiator: ammonium persulfate APS emulsifying agent: OP-10 SDS H 2O | 52.5 15.75 0.38 1.75 3.5 200 |
Second step: the preparation of core-shell type emulsion particle emulsion
The preparation method is with embodiment 1, feeds intake by the proportioning raw materials of table 5.
The prescription of the hud typed latex particle of table 5 preparation
| Raw material | Quality (g) |
| Monomer: Is nuclear emulsion emulsifying agent: OP-10 SDS initiator: ammonium persulfate APS H 2O | 20 200 0.67 1.33 0.6 150 |
By above two the step prepare particle diameter at 60～90nm, solid content is 21% hud typed latex particle.Wherein stratum nucleare is 5: 2 with the ratio of shell monomers.
Hud typed latex filler dosing in butadiene-styrene rubber
Addition methods is with embodiment 1.
The comparison of the styrene-butadiene rubber(SBR) mechanical property that different fillers of table 6 and addition methods obtain
All show tangible reinforced effects with respect to all fillers of pure styrene-butadiene rubber(SBR) (SBR) as can be seen from Table 6, wherein adopt the latex coprecipitation method to dose comprehensive mechanical property the best of the styrene-butadiene rubber(SBR) of hud typed latex particle.Because the linking agent DVB consumption of embodiment 2 center emulsions is greater than embodiment 1 consumption, the crosslinking degree height of embodiment 2 center latex particles, so the mechanical property of having dosed the styrene-butadiene rubber(SBR) of hud typed latex filler in the table 6 is better than embodiment 1.
Embodiment 3
The first step: the preparation of nuclear emulsion
Press the prescription of table 7, in reactor, add emulsifying agent MS-1 and deionized water (H
2O), stirring makes emulsifier mix even, and (α-MS) and vinyl cyanide (AN) and linking agent DVB stir and make monomer emulsification to add the monomer αJia Jibenyixi by a certain percentage, stablized after being warming up to 85 ℃ 10 minutes, with initiator ammonium persulfate (APS) with adding behind the deionized water dissolving.Holding temperature adds pH regulator agent sodium bicarbonate (NaHCO simultaneously
3), regulate pH=7; Reacted 6 hours, this moment, the monomer residue smell disappeared substantially, stopped polymerization.
The basic components of table 7 preparation α-MS-AN multipolymer nuclear emulsion
| Title | Quality (g) |
| Monomer: α-MS AN polyenoid class cross-linking monomer: DVB initiator: APS emulsifying agent: MS-1 H 2O | 30 20 10 0.6 4.5 110 |
Second step: the preparation of core-shell type emulsion particle emulsion
The prescription of pressing table 8 is under agitation condition, emulsion (the first step makes), isoprene (Is) are examined in adding in autoclave, (elder generation adds 2/3 to add emulsifying agent MS-1 at twice, emulsification adds in addition 1/3 again after 30 minutes), water, fully emulsified back adds initiator potassium persulfate KPS, with sodium bicarbonate (NaHCO
3) regulate pH=7, to pressurize 450 kPas, swelling 2.5 hours is warming up to 80 ℃, reacts 7 hours; Obtain core-shell type emulsion particle emulsion.
The basic components of the hud typed latex particle of table 8 preparation
| Title | Quality (g) |
| Monomer: Is nuclear emulsion emulsifying agent: MS-1 initiator: KPS H 2O | 30 200 2 0.53 200 |
By above two the step prepare particle diameter at 60～90nm, solid content is 25% hud typed latex particle.Wherein stratum nucleare is 5: 3 with the ratio of shell monomers.
Hud typed latex filler dosing in butadiene-styrene rubber
First method: the latex coprecipitation method, respectively according to 3: 10 mass ratio with the core-shell type emulsion particle emulsion and the SBR emulsion uniform mixing that make, use 5%CaCl again
2With the blended liquid breakdown of emulsion, every performance of test styrene-butadiene rubber(SBR) after vulcanizing.
Second method: melt-blending process, be used for the direct breakdown of emulsion of rubber enhanced core-shell type emulsion particle emulsion with what make, obtain solid particulate, again with itself and butadiene-styrene latex with 3: 10 quality than mechanical stirring, uniform mixing.After vulcanizing, test every performance of styrene-butadiene rubber(SBR) then.
Different fillers of table 9 and addition methods are to the comparison of the styrene-butadiene rubber(SBR) mechanical property that obtains
Annotate: α-MS-AN/Is is to be nuclear with αJia Jibenyixi and acrylonitrile copolymer, and isoprene is the hud typed latex particle of shell.
As can be seen from Table 9, dosed hud typed latex particle styrene-butadiene rubber(SBR) mechanical property aspect elongation at break and the tension set apparently higher than the value of having dosed with umber sooty styrene-butadiene rubber(SBR).
Claims (2)
1. preparation method who is used for rubber enhanced core-shell type emulsion particle emulsion:
The first step: under agitation condition, in reactor, add deionized water, emulsifying agent, alkene class hard monomer, polyenoid class cross-linking monomer successively and carry out emulsification, be heated to 70～85 ℃, add the initiator initiated polymerization, regulate pH=7, finished stratum nucleare particle building-up reactions, and obtained examining emulsion in 6-8 hour;
The mass ratio of used alkene class hard monomer, polyenoid class cross-linking monomer, initiator is 40～55:10～16:0.3～0.6;
Described alkene class hard monomer is any in the following material or their combination: vinylbenzene, methyl methacrylate, alpha-methyl styrene, glycidyl methacrylate, uncle's hendecoic acid vinyl acetate, acrylonitrile monemer;
Polyenoid class cross-linking monomer is any in the following material or their combination: Vinylstyrene, bisacrylamide, ethylene glycol dimethacrylate, tirethylene glycol dimethacrylate;
Second step: under agitation condition, in autoclave, add nuclear emulsion, shell diolefinic monomer, emulsifying agent, water and initiator that the first step makes successively, under agitation carry out emulsification, regulate pH=7,450-550 kPa of reactor pressurization, swelling 1～3 hour is warming up to 70～85 ℃, reacts 6-8 hour;
Described shell diolefinic monomer is any in the following material or their combination: isoprene, divinyl, butadiene oligomer;
The mass ratio that the used the first step makes nuclear emulsion, shell diolefinic monomer, initiator is 150～200:10～30:0.3～0.6.
2. according to the preparation method of claim 1, it is characterized in that: the used initiator of preparation emulsion particle emulsion is Potassium Persulphate, Sodium Persulfate, ammonium persulphate, Potassium Persulphate-sodium bisulfite, Sodium Persulfate-sodium bisulfite or ammonium persulfate-sodium bisulfite, the consumption of initiator in the first step reaction is 0.7%～1.2% of alkene class hard monomer quality, and the consumption in the reaction of second step is 1%～2% of a shell diolefinic monomer quality.
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| CN101638453B (en) * | 2008-07-31 | 2012-05-09 | 于景东 | Modified pyridine styrene butadiene rubber latex and preparation method and application thereof |
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| EP3239198B1 (en) | 2014-12-24 | 2019-03-06 | LG Chem, Ltd. | Method for preparing diene-based rubber latex and acrylonitrile-butadiene-styrene graft copolymer comprising the same |
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| CN106749827A (en) * | 2016-12-27 | 2017-05-31 | 宁波高新区敦和科技有限公司 | A kind of nano-functional macromolecular material and preparation method thereof |
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| CN110407987B (en) * | 2019-07-08 | 2022-02-01 | 联泓(江苏)新材料研究院有限公司 | Acrylic emulsion and preparation method and application thereof |
| CN113072752B (en) * | 2021-04-01 | 2022-11-22 | 西南科技大学 | Rubber composite material with excellent nuclear protection and flexibility and preparation method thereof |
| CN116463021B (en) * | 2023-06-20 | 2023-09-19 | 富维薄膜（山东）有限公司 | Water-based coating liquid, preparation method and application thereof in non-silicon release film |
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